CN106393539A - Polymer foam and method for preparing the same - Google Patents

Polymer foam and method for preparing the same Download PDF

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Publication number
CN106393539A
CN106393539A CN201610598896.7A CN201610598896A CN106393539A CN 106393539 A CN106393539 A CN 106393539A CN 201610598896 A CN201610598896 A CN 201610598896A CN 106393539 A CN106393539 A CN 106393539A
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CN
China
Prior art keywords
polymer
pif
pressure
pore
micro
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Granted
Application number
CN201610598896.7A
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Chinese (zh)
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CN106393539B (en
Inventor
李利
李大超
严英杰
付大炯
邱媛媛
林江祥
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LCY Chemical Corp
Ohio State Innovation Foundation
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LCY Chemical Corp
Ohio State Innovation Foundation
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Publication of CN106393539A publication Critical patent/CN106393539A/en
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Publication of CN106393539B publication Critical patent/CN106393539B/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/60—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3415—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B29C44/3453—Feeding the blowing agent to solid plastic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • B29C67/207—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising impregnating expanded particles or fragments with a binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/06—PVC, i.e. polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/041—Microporous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/048—Expandable particles, beads or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/004—Semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0077—Yield strength; Tensile strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Polymer foam and a method for preparing the same are disclosed. In the present disclosure, the method sequentially comprises the following steps: providing a polymer body; performing a pressure-induced flow (PIF) process on the polymer body at a first predetermined temperature and a first predetermined pressure for a pressure holding time, to obtain a polymer sheet; and performing a foaming process on the polymer sheet by using a foaming agent at a second predetermined temperature and a second predetermined pressure for a saturation time, to obtain polymer foam.

Description

Micro-pore of polymer and preparation method thereof
Technical field
The present invention is with regard to a kind of method for preparing micro-pore of polymer, more specifically, being through pressure with regard to a kind of Power induced flow (pressure-induced flow, the PIF) method to prepare micro-pore of polymer for the step.
Background technology
Micro-pore of polymer, particularly polypropylene (polypropylene) foaming body, has answering in many task industry With global micro-pore of polymer market has witnessed the Fast Growth between the past few years.
Polypropylene (PP), as one of most widely used commercial polymer, has many preferably characteristics, such as Gao Rong Point, good plasticity, low-density, excellent chemical resistance and foodsafety, and easily reclaim.These outstanding spies Property and low material cost make polypropylene (PP) compared to other thermoplastics in various commercial Application, produce plastics and Foaming body product aspect has more competitiveness.However, such as other commercial polymers, the low thermal stability of polypropylene (PP) and low machine Tool intensity hinders it in the application of many engineerings and configuration aspects.Additionally, being combined or use unless there are long link, polymer It is chemically crosslinked and to modify polypropylene (PP), otherwise in flux foaming step, the low melt strength of polypropylene (PP) can lead to steep Body (cell) rupture and low ratio foamed multiplying power.
However, because low melt strength and high-crystallinity make polypropylene (PP) be very difficult to foam.Many methods are such as:Poly- Compound blend, composite and combined polymerization have been used for obtaining good expandable polypropylene (PP) and polypropylene (PP) foaming body.But because the mechanical strength of the significant increase of material cost and foaming body product in than polypropylene (PP) and other The difference that the foam material being widely used such as polystyrene (PS) comes is so that the application of said method is limited to.
Therefore, that needs a kind of novelty of offer badly prepares micro-pore of polymer, the particularly method of polypropylene (PP) foaming body, It to be hopeful most and can prepare micro-pore of polymer in the way of most viable；And the micro-pore of polymer therefore, being obtained Can successfully be applied on industrial products.
Content of the invention
One purpose of the present invention be to provide a kind of through a pressure-induced flow (pressure-induced flow, PIF) the method that step and a foaming step prepare micro-pore of polymer.
Another object of the present invention is to providing a kind of micro-pore of polymer being obtained by the method for the present invention.
Additionally, a further object of the present invention is to provide one kind to have altogether through the preparation of pressure-induced flow (PIF) step The method of the polymer sheet of continuous structure (co-continuous structure).
In an example of the present invention, the method preparing micro-pore of polymer comprises the following steps：There is provided a polymer originally Body；Under one first specified temp and one first specified pressure, in one specific hold the pressure time, this polymer body carries out one Pressure-induced flow (PIF) step is to obtain a polymer sheet；And in one second specified temp and one second specified pressure Under, in a saturation time, a foaming agent is injected on this polymer sheet and carries out a foaming step to obtain polymer foaming Body.
In another example of the present invention, preparation has the poly- of co-continuous structure (co-continuous structure) The method of compound sheet material comprises the following steps：There is provided a polymer complex, it includes polymer beads and coating material, and It is coated with coating material on the surface of these polymer beads；And under one first specified temp and one first specified pressure, In one specific hold the pressure time, a pressure-induced flow (PIF) step is carried out on this polymer complex and has altogether to obtain one The polymer sheet of continuous structure.Additionally, when the polymer sheet with co-continuous structure of above-mentioned acquisition, specific one second At temperature and one second specified pressure, in a saturation time, when injection one foaming agent is to carry out a foaming step, can obtain poly- Polymer composite foaming body.
In another example of the present invention, the micro-pore of polymer being obtained includes：One polymer body, this polymer is originally There are in body multiple foams (cell), wherein this micro-pore of polymer has expansion density between 0.03g/cm3To 0.25g/cm3 Between；And when the compressive strain (compressive strain) of this micro-pore of polymer is between 10% and 70% When, this micro-pore of polymer has compressive strength (compressive strength) between 0.2MPa to 0.7MPa.
Existing not modified polymer, particularly virgin pp (neat polypropylene), because its low melt The reason of intensity and high-crystallinity and be difficult to foam.There is provided a kind of method of novelty in the present invention, wherein polymer is to pass through Pressure-induced flow (PIF) step and foaming step and foam.By utilizing the method for the present invention, this polymer can be less tight Under conditions of severe (lower pressure and higher temperature) and saturation time short in the case of foam with obtain have high performance low close Degree micro-pore of polymer, but the invention is not restricted to this.Therefore, compared to traditional step preparing micro-pore of polymer, this Pressure in bright method and saturation time can reduce；Therefore, the method for the present invention is more suitable for manufacturing polymerization in commercial Application Thing foaming body.
Additionally, compared to the conventional composite thing being formed by same composition thing and foaming body, when this polymer composites, (it includes Polymer beads and be coated on the coating material on this polymer beads) through pressure-induced flow (PIF) step and optionally During foamed step process, obtained there is the polymer sheet of co-continuous structure or foaming body structure can show excellent Machinery and physical characteristics.
Additionally, compared to the traditional polymer foaming body being obtained without pressure-induced flow (PIF) step, the present invention's is poly- Compound foaming body has low ratio foamed density and high intensity simultaneously.Therefore, the micro-pore of polymer prepared with the inventive method can Further apply in various industrial products.
In the micro-pore of polymer of the present invention and method, this polymer body can simply by polymer, or This polymer body can be a kind of polymer complex, and this polymer complex includes polymer beads and is coated on this polymer Coating layer on particle surface.When polymer body used in the inventive method is above-mentioned polymer complex, this gathers Polymer composite can be prepared by following step：There is provided and mix this polymer beads and this coating material to obtain a mixing Thing；And heat this mixture to obtain this polymer complex, wherein this polymer complex include this polymer beads and by The coating layer that coating material is formed.After this mixture is heated, the polymer composites being obtained have a honey comb structure (honeycomb-like structure).
Here, this polymer beads and this coating material can be mixed at a temperature of between 140 DEG C to 160 DEG C. In order to help mix, grinding agent such as Zirconia reinforced alumina (zirconia toughened alumina) can be added, so Mixing can be made more uniformly and thorough.Additionally, this mixture can be heated at a temperature of 100 DEG C to 300 DEG C；And can be Heat this mixture under the pressure of 11.7MPa to 17.3MPa.Here, the heating means being used can for hot gas, electrical heating, Infrared ray or microwave.Additionally, the polymer complex being obtained can be further transmitted through sieve to remove grinding agent and to remain Remaining coating material.
Furthermore, there is no particular restriction for the coating thickness on this polymer beads, is about 1 μm to 1000 μm.Additionally, root According to by coating material coating step on the polymer particles, temperature and/or pressure, this coating layer can be completely or partially embedding Enter the inner side on the surface of this granule, or can be attached on the surface of this granule.
In the method for the present invention, this polymer body can be in the temperature (such as, 210 DEG C) higher than room temperature and pre- level pressure Under power (such as 1700psi), optionally it is pressed into flat piece, membranaceous or other shapes in advance.However, this step non-invention Method necessary step, this polymer body can directly carry out pressure inducement stream in the case of not carrying out above-mentioned pressing step Dynamic (PIF) step.
In the method for the present invention, this first specified temp in pressure-induced flow (PIF) step depends on polymerization The type of thing body, and preferable system is less than the fusing point of this polymer body.This first specified temp is preferably between 100 DEG C extremely 160℃.This first specified temp is more preferably between 110 DEG C to 150 DEG C.Most preferably, when polymer body is to be made up of PP, on The first specified temp stated is the temperature being applied to PIF step.
In the method for the present invention, this first specified pressure in pressure-induced flow (PIF) step can be between 20MPa To 420MPa.This first specified pressure preferably can be between 20MPa to 200MPa.This first specified pressure more preferably can be between 20MPa To 50MPa.When pressure-induced flow (PIF) step for the method for the present invention is ultrasonic assistant pressure-induced flow (UAPIF), during step, this first specified pressure can be further reduced.
In pressure-induced flow (PIF) step, holding the pressure time is not particularly limited, as long as this polymer body energy Enough deform.This holds the pressure time preferably between 10 seconds to 300 seconds.This holds the pressure time more preferably between 10 seconds to 30 seconds.
In the method for the invention, after above-mentioned pressure-induced flow (PIF) step is finished, the knot of polymer body Crystalline region domain can be changed into a kind of co-continuous " brick and mud " shape structure.
In the method for the invention, this in foaming step second specified temp can be between 120 DEG C to 180 DEG C.This Two specified temps preferably can be between 130 DEG C to 160 DEG C.This second specified temp more preferably can be between 140 DEG C to 155 DEG C.
In the method for the invention, this in foaming step second specified pressure can be between 11MPa to 20MPa.This Two specified pressure preferably can be between 11.7MPa to 17.3MPa.This second specified pressure more preferably can between 13.8MPa extremely 17.2MPa.
In foaming step, saturation time is not particularly limited, as long as the foaming that this polymer sheet can be certain ?.This saturation time can change with the thickness of polymer sheet.In the present invention, this saturation time preferably 10 minutes To 2 hours.
In the foaming step of the method for the present invention, there is no particular restriction for the foaming agent being used, can for any gas or It is the material that can discharge gas.The example of this foaming agent includes but is not limited to：Pentane (pentane), isopentane (isopentane), Pentamethylene. (cyclopentane), CO2、N2, nitride materials (nitrogen-based material) or A combination thereof.It is preferred that the foaming agent being suitable for the method for the present invention is CO2.This foaming agent most preferably supercritical carbon dioxide (supercritical CO2).
Here, this foaming agent can be imported in the reactor for carrying out foaming step, or using single device, example As extruder or kneader, import polymer body before carrying out PIF or foaming step.
In the micro-pore of polymer of the present invention, this micro-pore of polymer can have expansion density between 0.03g/cm3Extremely 0.25g/cm3.Preferably, this expansion density is between 0.04g/cm3To 0.10g/cm3Between.Therefore, obtained in the present invention Polymer foaming system one low-density polymeric foaming body.
In the micro-pore of polymer of the present invention, when micro-pore of polymer is placed on 120 DEG C of condition, this polymer is sent out The absolute value of one change in size of foam between 0% to 60%, and preferably between 0% to 40%.
In the micro-pore of polymer of the present invention, this micro-pore of polymer can have degree of crystallinity between 10% to 30%.Relatively Good is that the degree of crystallinity of this foaming body is between 15% to 25%.
In the micro-pore of polymer of the present invention, these foams (cells) can have 200 μm to 300 μm of average foam Size.Preferably, the average foam size of these foams is between 240 μm to 260 μm.
In the micro-pore of polymer of the present invention and method, the species of this polymer body or this polymer beads has no spy Other restriction, and can be semicrystalline thermoplastics or thermoplastic elastomer (TPE).Semicrystalline thermoplastics or thermoplastic elastomer (TPE) Instantiation can be polyolefin (polyolefins), it may include but be not limited to, and at least one is selected from polyethylene (polyethylene), polypropylene (polypropylene) (including homopolymer, block copolymer or Random copolymer RCP), poly- Vinyl chloride (polyvinyl chloride), Merlon (polycarbonates), polyamide (polyamides), poly- to benzene Dioctyl phthalate second diester (polyethylene terephthalate), polybutylene terephthalate (polybutylene ) and the group that formed of polylactic acid (polylactic acid) terephthalate.The example of this thermoplastic elastomer (TPE) can Include, but are not limited to：Polyolefin blends, elastomer alloy (TPE-v or TPV) and polyamide thermoplastic.Additionally, these polymerizations There is no particular restriction for the shape of composition granule and size.In the method for the present invention, this polymer body is not preferably modified Polymer.This polymer body or this polymer beads more preferably include virgin pp (neat PP).Above-mentioned " virgin pp " means Not modified PP.
Additionally, the coating material of this polymer complex can be an organic substance, inorganic substances or a combination thereof.This has The example of machine material include, but are not limited at least one selected from carbon nano-particle, carbon particulate, Graphene, graphene oxide, The group that carbon black, carbon nano-fiber, CNT and graphite are formed.The example of this inorganic substances includes, but are not limited at least One kind is selected from clay, Muscovitum, glass fibre, silicate, metallic particles, SiO2, MgO, CaO, Pulvis Talci, TiO2, ZnO and MnO The group being formed.
Brief description
Figure 1A is the schematic diagram of the PIF device that one embodiment of the invention is used；
Figure 1B is PP sample through the schematic diagram before PIF step process and after process；
Fig. 2A be the embodiment of the present invention 1 PIF step after part PP sample schematic diagram；
Fig. 2 B be the embodiment of the present invention 1 foaming step after part PP foaming body schematic diagram；
Fig. 3 is the XRD of the PP sample through PIF step process under 150 DEG C and 34.5MPa for the embodiment of the present invention 1；
Fig. 4 is the relation with expansion density for the blow pressure of the embodiment of the present invention 1；
Fig. 5 is the schematic diagram of the thermal characteristicss processing PP foaming body in the embodiment of the present invention 1 with different blow pressures；
Fig. 6 is scCO in the embodiment of the present invention 12Saturation time is for the effect of expansion density；
Fig. 7 A to 7C is in the embodiment of the present invention 1, the PIF PP foaming of formation under the conditions of different pressures and different saturation time The SEM of body；
Fig. 8 is the schematic diagram of the compression behavior of various foaming bodies of the embodiment of the present invention 1；
Fig. 9 is the schematic diagram of the heat stability of various foaming bodies of the embodiment of the present invention 1；
Figure 10 A is the schematic diagram of the PP/MWCNT complex that the embodiment of the present invention 2 is obtained；
Figure 10 B is in the embodiment of the present invention 1, the schematic diagram of part PP/MWCNT sheet material after PIF step；
Figure 10 C is in the embodiment of the present invention 2, the schematic diagram of part PP/MWCNT foaming body after foamed step；
Figure 11 A and 11B is respectively the polarizing microscope through PP sample before PIF step process and afterwards for the embodiment of the present invention 2 Image；
Figure 12 A is the DSC of original PP, PIF PP, UAPIF PP and PIF PP foaming body that the embodiment of the present invention 2 is obtained Curve；
Figure 12 B is the XRD of the original PP and PIF PP that the embodiment of the present invention 2 is obtained；
Figure 12 C is that the temperature in UAPIF step rises；
Figure 13 A to 13C represents in the embodiment of the present invention 2 respectively, PP and PP/MWCNT obtained via PIF or without PIF answers The schematic diagram of the pulling force of compound, bending and impact strength；
Figure 14 is the flexural property schematic diagram of the pure PP and UAPIF-PP/MWCNT complex that the embodiment of the present invention 2 is obtained；
Figure 15 is the schematic diagram of the expansion ratio of pure PP foaming body that the embodiment of the present invention 2 is obtained and PIF PP foaming body；
Figure 16 is thermo-mechanical analysis (TMA) curve of pure PP and PIF-PP foaming body；
Figure 17 A and 17B be respectively via PIF step and without PIF step derived from nano combined of pure PP and PP/MWCNT The compression stress of the high density of foam and low-density PP foaming body and compressive strain curve；
Figure 18 A and 18B is the TMA curve of pure PP and PIF PP in the embodiment of the present invention 2；And
Figure 19 A and 19B is in the embodiment of the present invention 2, with PP and PP/MWCNT 3wt% pure after UAPIF step process be combined curved Transverse stress.
【Description of reference numerals】
11 channel-shaped moulds
111 die cavitys
13 plungers
210 polymer beads
220 coating layers
230 foams
3 test pieces
3 ' sheet materials
310 test pieces
330 foams
LD load direction
CD limits direction
FD flow direction
Specific embodiment
For making the object, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, and with reference to attached Figure, the present invention is described in further detail.
Figure 1A is the schematic diagram of PIF device used in the present invention.The PIF device that this is used for the present invention mainly includes：One channel-shaped Mould 11, this channel-shaped mould 11 has die cavity 111；And a plunger 13, this plunger 13 has the chi roughly the same with die cavity 111 Very little.In PIF step, sample 3 is placed in die cavity 111, then extruding is heated with plunger 13；Subsequently, sample 3 produces deformation, Flowed into flow direction (FD), and be limited in restriction direction (CD) and in load direction (LD) compression.Figure 1B is sample treatment Front and schematic diagram after PIF step.Sample 3 before through PIF step process has a cubic shaped；But the present invention is not It is limited to this.After PIF step, this sample 3 is squeezed into sheet material 3 '.
In ensuing embodiment, the size of die cavity 111 is 100 × 12 × 12mm, but the invention is not restricted to this.
Embodiment 1- only prepares micro-pore of polymer with polypropylene (PP)
Identification
Expansion density：Mass density ρ of the PP sample being obtainedfSystem measures according to ASTM D792, and it is to utilize sinker Weighing micro-pore of polymer in water.ρfIt is calculated as follows：
Wherein a is the aerial apparent mass of sample, and b is completely immersed in the apparent mass in water for sample.
Scanning electron microscope (SEM)：Observe the form (Philips XL30) of the PP foaming body obtaining with SEM.This sample Product are immersed in liquid nitrogen 30 minutes and rupture.This plane of disruption is plated one layer of gold to further look at through SEM.
Thermo-mechanical analysis (TMA)：Observe PIF and foaming body sample using TMA (TA Instruments TMA 2940) Heat stability.Under the pattern that penetrates with 5 DEG C/minute of scan speed measurement sample the change in size from 30 DEG C to 180 DEG C.
Differential scanning calorimeter (DSC)：TA Q200 DSC is used for the qualitative PP foaming through PIF step or without PIF step Body melting behavior.Sweep limitss system from 20 to 200 DEG C, 10 DEG C/minute of speed.Sample is cut into the thin slice of 6-10mg to carry out DSC is qualitative.
X-ray diffraction (XRD)：Using there is Cu-k alpha ray source and X-ray wavelength isX-ray diffractometer (Bruker D8 Advance XRD) studies crystal structure.Under 40V and 50mA, from 5 ° to 45 ° with 4 °/minute rate scannings This sample.
Compression test：The compressive strength system of foaming body is with Instron5569 advanced material test system (Instron 5569 Advanced Materials Testing system) measured according to standard ASTM D695 at room temperature.
Experiment
PP and PIF condition is for the impact of expansion density
Here, having listed the variety classes PP with different melt flow index (MFI) being used in table 1.By size PP sample for 50mm (length) × 12mm (wide) × 2mm (high) is positioned in the PIF device shown in Figure 1A, and arranges in Table 1 Various different temperatures, different pressures and the difference shown holds deformation under the pressure time.Fig. 2A system part PP sample after PIF step 310 schematic diagram.
After PIF step, obtained sample is placed in high-pressure bottle, subsequently in this high-pressure bottle, injection purity is 99.99% scCO2.After sample saturation certain time under a specified temp and pressure, moment blood pressure lowering is to realize PP foaming. The schematic diagram of part PP sample 310 after Fig. 2 B system foaming step.As shown in Figure 2 B, after foaming step, formed in PP sample 310 Foaming body (cell) 330.
In the present embodiment, result is simultaneously summarized in table 1 below by the obtained expansion density of PP sample of detection.
Table 1
Foaming condition：155 DEG C, 13.8MPa, 2 hours；N/A：Cannot foam
PP1:Pure PP, PC366-3 (HOPP), are provided by Lee Chang Yung Chemical Indust
PP2:Pure PP, PT100 (HOPP), are provided by Lee Chang Yung Chemical Indust
PP3:Pure PP, 6331 (HOPPs), provided by Lee Chang Yung Chemical Indust
PP4:Pure PP, HP600S (HOPP), are provided by Lee Chang Yung Chemical Indust
Dow PP:H349-02 (HOPP), is provided by Dow Chemical
As shown in table 1 it can be seen that the PP with low MFI shows preferably foam characteristics.Increase with MFI, represent Melt strength, PP still can foam, but expansion density increased.Business-like high melt strength, propylene (HMSPP) (WB140 is purchased from Borealis) is also used as comparing：Foaming that also can be good when without PIF, but foaming body intensity and heat Stability is not good, as can be seen from figures 8 and 9.
Relatively as PP fiber and this kind of orientation of Biaxially oriented polypropylene (BOPP) thin film, there is " shish-kebab structure (shish- Kebab structure) " PP product.The result display PP fiber of table 1 and BOPP all cannot foam, and imply that only orientation Crystal structure is not enough to carry out PP foaming.Obviously, elongated " brick and mud (brick and the mud) " shape being formed by PIF step Crystal structure is necessary for reaching PP foaming.
In order to carry out PIF, temperature have to be lower than the fusing point of PP, and therefore in whole PIF step, PP remains in that solid, shaped State.Suitable pressure and at a temperature of, PP amorphous area deforms along applying stressed vertical direction to extend the spherocrystal region of PP (spherulite crystal domains), has trade-off relation between the temperature applying and pressure.At low temperature, need Using higher pressure；If using higher temperature, even if being also to reach similar effect under low pressure.
Hereinafter, the PP1 that selection table 1 is listed optimizes PIF and foaming step further.PIF condition lists in table 2, Carry out aforesaid foaming step, similarly maintain foaming condition in 13.8MPa and 155 DEG C, 2 hours.
Table 2
PIF condition The PIF time Expansion density (g/cm3)
110℃,414MPa 300 seconds 0.043
110℃,414MPa 10 seconds 0.073
150℃,34.5MPa 300 seconds 0.052
150℃,34.5MPa 10 seconds 0.094
As shown in table 2, in 150 DEG C and 34.5MPa, the density of the foamed sample through PIF step process closely 110 DEG C and situation during 414MPa.And, it is often little for expansion density impact that PIF holds the pressure time.Mean many task industry Relevant PIF condition, the pressure time of holding that 34.5MPa replaces 414MPa pressure and replaces 300 seconds in 10 seconds has sufficiently achieved low-density PP foaming body.In other words, the cycle time of PIF can shorten many.Fig. 3 is to be walked with PIF under the conditions of 150 DEG C and 34.5MPa The XRD figure of the rapid PP sample processing, and this result shows 34.5MPa and 150 DEG C and spherocrystal observed by 414MPa and 110 DEG C Deformation is similar.
Blow pressure is for the impact of expansion density
In foaming step, blow pressure is a key factor.Different blow pressures is used for studying for expansion density Impact.Hereinafter, select table 1 in PP1, PIF condition be 150 DEG C, 34.5MPa and 10 second, and foaming condition be 155 DEG C, 2 Hour and different blow pressures (8.3,11.7,13.1,13.8,15.5 and 17.3MPa).
As shown in figure 4, expansion density declines suddenly generation in 13.8MPa.When pressure is less than 13.8MPa, expansion density Higher.During higher than 13.8MPa, increase with pressure, expansion density remains unchanged substantially.Here, the degree of crystallinity of foaming PP sample Also detected with DSC and result is summarised in table 3.
Table 3
As shown in upper table 3, the obvious change of foaming body degree of crystallinity can be observed.During below 13.8MPa, the knot of PP foaming body Brilliant degree is similar, and when pressure reaches 13.8MPa, observable degree of crystallinity significantly declines.Known melt temperature can be with CO2Full Reduce with the increase of pressure.Obviously, when pressure is less than 13.8MPa, the melt temperature of PP declines, but still higher than 155 DEG C Blowing temperature.In the case, for the amorphous area still very little of foaming, therefore expansion density is high.However, working as CO2Saturation pressure When power reaches 13.8MPa or more, melt temperature becomes close to 155 DEG C, and substantial amounts of crystalline fusion becomes amorphous phase.Net result is Work as CO2During saturation pressure release, expansion density suddenly declines.Higher blow pressure also implies that higher pressure is released simultaneously Put speed, in foaming step, therefore have more foam nucleation and grow up.
The thermal characteristicss schematic diagram of the foaming PP that Fig. 5 system is processed with different blow pressures.As seen from Figure 5, work as CO2 When saturation pressure is less than 13.8MPa, crystalline melting peak has almost no change.With CO2Saturation pressure increases to 13.8MPa and surpasses Cross 13.8MPa threshold value when, in 155 DEG C of isothermal CO2Little melting peak shoulder occurs in saturation process, represents faulty crystal Fusing and recrystallization.Being left those crystallizations unfused can be α1To α2Crystallize improves form, and it has higher fusing temperature Degree, can be in 155 DEG C of high CO2Retain under saturation pressure.Remaining elongated " brick " shape crystal structure for the foaming of PP is Important.In heat absorption foaming step, cooling step is very quick, therefore, melts crystal and some possible amorphous phases There is recrystallization and rearrange, lead in higher CO2The degree of crystallinity of saturation pressure is increased slightly, as shown in table 3.
CO2Saturation time is for the impact of expansion density
In foaming step, CO2Saturation time can affect expansion density.Because when batch foaming generally needs longer gas saturation Between, it is a kind of time-consuming step, therefore shortening saturation time is non-the normally off key for plant-scale batch foaming process. Study the impact of the expansion density for the PP through PIF step for the different saturation times, and result is shown in figure 6, wherein Foaming condition is 155 DEG C and 13.8MPa.As shown in fig. 6, saturation time length corresponds to low ratio foamed density, represent higher foaming Multiplying power.However, for given sample size, when saturated between the plateau of expansion density can be observed when being longer than 10 minutes Phase.This result represents when pressure is released, and the PP through PIF step can keep CO2And avoid CO2Loss from PP substrate.For It is favourable for reaching low density foaming agent within the short batch foaming cycle time.
The form of PIF PP foaming body
Observe the form of PIF PP foaming body through SEM, result is as shown in the figure.Fig. 7 A to 7C is to be observed using SEM PIF PP foaming body (as shown in Figure 7 A) that 11.7MPa pressure was formed under the conditions of 2 hours, works as CO2Saturation pressure is less than During the key value of 13.8MPa, the little foam of only minority is present in foaming body and expansion density is high.Work as CO2Saturation pressure reaches To the key value 2 hours of 13.8MPa, can obtain foam density is 2.75 × 106Very low density foaming agent, as Fig. 7 B institute Show.And when can be observed within 2 hours under 13.8MPa pressure there is equally distributed foam in foaming body, and those foams is flat All a size of 261.5 μm.As seen in figure 7 c, in terms of the SEM result in the PIF PP foaming body of 13.8MPa pressure foaming in 10 minutes Come, shorter saturation time can reach similar to having slightly higher foam density (5.2 × 106) and slightly smaller foam size (255 μ M) PP foaming body.
The compression behavior of PP foaming body
The compressive strength of foaming body is a key factor to be considered in practical application.13.8MPa, 155 DEG C carry out After foaming step, the compression behavior of test PP foaming body, result is as shown in Figure 8.With under saturation time 2 hours and 10 minutes PIF PP foaming body is as comparing.Compared to pure PP foaming body and WB140 HMS PP, PIF PP foaming body has higher pressure Contracting intensity.The PIF foaming body being formed in different saturation times then has similar compressive strength.
The heat stability of PIF PP foaming body
Heat stability is also to determine one of most important factor of foaming body application.Fig. 9 is the TMA result being obtained.For It is compared, the high fondant-strength PP (HMSPP) of coffee cup will be used for and surveyed in the lump for heat-insulating PS foaming body Examination.Obviously, under similar expansion density, PIF PP foaming body has higher heat stability and reaches more than 100 DEG C in temperature When foaming body will not collapse.Represent PP foaming body through PIF step and there is higher operating temperature and preferably compressive strength, Multiple different working environments can be met and there are the potentiality replacing traditional EPP and PS foaming body, particularly mainly need to consideration Those learning toxicity are used as the application of food container.
From the result of embodiment, the PP through PIF can be under the low pressure of 34.5MPa and 10 seconds low was held under the pressure time Carry out.In XRD analysis it was observed that spherocrystal deformation, even if represent under the conditions of so gentle PIF, be still formed with PP " brick and mud " structure of orientation.Additionally, from the result of the present embodiment, in order to foam at 155 DEG C, the critical CO of 13.8MPa2Saturation Pressure is necessary for reaching low-density PP foaming body.Additionally, for the thick sample of 2-mm, also finding for PIF PP The CO of foaming2Saturation time significantly can shorten to 10 minutes from 2 hours.Compared to traditional PP foaming body, PIF PP sends out Foam shows higher compressive strength and preferably heat stability.Therefore, the permeable present invention of PP foaming body is hopeful and can The method of row is manufactured.
The preparation of embodiment 2- includes PP and the compound micro-pore of polymer of multi-walled carbon nano-tubes (MWCNT)
Identification
All qualitative methods for the present embodiment to similar described in embodiment 1, discrepancy is shown in down.
SEM：Difference between embodiment 1 and the present embodiment is that the present embodiment is that sample is immersed in 10 points in liquid nitrogen Clock simultaneously ruptures.
DSC：Difference between embodiment 1 and the present embodiment is that the present embodiment is that sample is cut into the thin of 10-15mg Piece is qualitative to carry out DSC.
XRD：Difference between embodiment 1 and the present embodiment is that the present embodiment is with 0.4 ° of incremental scan from 5 ° to 70 ° This sample.
Polarizing microscope：Prepare PP sample sheet using Leitz 1720 Cryostat Microtome.PP sample is dropped Temperature, to -15 DEG C, is then cut into 25 to 50 μm of thin slice.This 25 μm thin slice utilize polarized light microscope observing PIF before and The crystal structure of PP sample afterwards.And 50 μm of thin slice then utilizes observation by light microscope PP sample, determine that its " brick and mud " is tied Structure.
Engineering propertiess are tested：All of sample is carried out with appropriate size by engineering propertiess test according to ASTM standard.Using INSTRON 5569 advanced material pilot system, the bending of test sample, pulling force and compression property at room temperature.Sample Izod impact strength (Izod impact strength) system utilizes TMI izod impact test instrument (TMI Izod Impact tester) measure at room temperature.The resistance of sample is then at room temperature with Keithley 6514 electrometer (Keithley 6514electrometer) records.
Experiment
Melt flow index is the Dow Chemical from the U.S. for the linear PP H349-02 system of 2.0g/10min.In nitrogen In gas, under normal pressure, under conditions of 10 DEG C/min sweep speed, its degree of crystallinity and melt temperature be 37.62 ± 0.02% and 164 ± 0.85℃.The original size of PP granule is between 2-2.5mm, and is ground into the more little particle that diameter is not more than 0.3mm.Yu Ben In the other embodiment of invention, a diameter of 0.01mm to 0.3mm of this abrasive grains.
A diameter of 10-15nm and pipe range are purchased between 0.1-10 μm of Graphistrength C100 multi-walled carbon nano-tubes GraphiSTRENGTH advanced material company (GraphiSTRENGTH Advanced Materials).
PP granule (60g), MWCNT (0.6-2.0g) and abrasive media (150g) will be ground and be positioned over a glass container (1000ml), in, carry out mechanical agitation (300rpm) in 135 DEG C.After 30 minutes, with various sizes of sieve, mixture is classified, obtain Obtain the PP through MWCNT coating.Figure 10 A is the polymer body schematic diagram of the PP/MWCNT complex that the present invention is obtained, wherein This polymer body includes the polymer beads 210 being formed by PP and a coating layer 220 being formed by MWCNT, and is coated with Layer 220 is formed on polymer beads 210.
Next, be placed on coated PP granule there is two Teflon processing release papers (Teflon mold release Papers) and between two blocks of aluminium sheets at interval (diameter 8cm, thickness 3mm).Combinations thereof is placed on 10MPa, is preheated to 200 DEG C molding apparatus (press).After 10 minutes, this molding apparatus is naturally cooled to room temperature and obtains the PP/ of honey comb structure MWCNT nano-complex.In order to be compared, using double screw extruder kneading PP/MWCNT (Leistriz Model2570, L/D=40, D=27mm).For there being enough mixing, extruder is constructed in relatively high rotary speed with co-rotating twin screw Under (60rpm) run.Heating-up temperature is maintained at 200 DEG C.Pure PP and PP/MWCNT complex test piece is then using molding at 200 DEG C Molding is obtained (Carver 3853).
Honeycomb PP/MWCNT nano-complex is processed to desired geometry, such as 3mm x 12mm x 25mm Test piece.Subsequently, test piece is inserted in die cavity, the such as die cavity of 12mm x 12mm x 100mm, then carry out PIF step.Plus Mold heat to specified temp, such as 110 DEG C when, then this mould and test piece are imposed with a very high static pressure (static Pressure), such as 400MPa.Flowed with importing test piece by applying pressure.Except the test piece through PIF step process Outward, carry out ultrasound wave using the ultrasonic activation instrument of Branson 921 aes (Branson Ultrasonics Corp.) auxiliary Help PIF (UAPIF) step.Except applying in addition to ultrasonic activation probe to test piece, remaining step is identical with PIF.Applying pressure The situation of the time (such as 4 seconds) of the frequency of vibration (such as 20khz) of (such as 20.7MPa), ultrasound wave and supersonic vibration Down so that test piece deforms or flows.The equal natural cooling of all test pieces through PIF and UAPIF step.In PIF or UAPIF step Afterwards, obtain PP/MWCNT sheet material, and its schematic diagram is as shown in Figure 10 B.In Figure 10 A and 10B, include the polymer being formed by PP Granule 210 and this polymer body being formed at the coating layer 220 being formed by MWCNT on polymer beads 210, tie up to through After crossing aforesaid PIF or UAPIF step, molded and form polymer sheet；Wherein this polymer sheet includes multiple such as figures Polymer body depicted in 10A links each other.
Next, before or after carrying out PIF or UAPIF, using batch foaming step by PP and PP/MWCNT complex system Produce foaming body.This PP nano-complex is placed in the steel cell body being preheated to blowing temperature (130-160 DEG C).Treat that temperature reaches After balance, by cavity seal and under 13.8MPa pressure, using syringe side Pu, carbon dioxide is injected this high pressure cell body In.Temperature and pressure is kept making CO in 2 hours2Diffusion, then discharges pressure to induce foam nucleation and foaming within the 2-3 second. PP/MWCNT foaming body can be obtained after foaming step, its schematic diagram such as Figure 10 C, plurality of foam 230 is to be formed at polymerization In composition granule 210.
In order to compare, the pure PP through compression molding preparation and compound PP/MWCNT nano-complex also pass through identical side Formula is carried out.The result of the present embodiment will be described in detail below.
" brick and mud " structure
Different with traditional spherulitic crystal structure, force PP test piece to make crystal along PIF's with solid state flowing under PIF Direction is orientated.From PP test piece 400MPa and 110 DEG C through PIF before processing and process after micropolariscope (POM) result, not PP test piece through PIF shows traditional spherulitic crystal structure, size about at 30-50 μm, as shown in Figure 11 A；And the PP examination through PIF Piece, its crystal is orientated along the direction of PIF, as shown in Figure 11 B.
Additionally, the crystal structure change through PIF is qualitative with differential scanning calorimeter (DSC) and X-ray diffraction (XRD).? This, qualitative PP, PIF PP (PIF condition：110 DEG C, 400MPa), UAPIF PP (PIF condition：110 DEG C, 20.7MPa) and PIF PP foaming body (foaming condition：13.8MPa,155℃).DSC result such as Figure 12 A, after PIF, melting peak and degree of crystallinity are equal for display Increase a little, respectively from 165.1 increase for 168.74 DEG C, 30.2% increase to 32%.XRD spectrum (the wherein non-PIF of Figure 12 B PP-0 ° and PP-90 ° of non-PIF of curve overlaps) show that the curve of non-PIF PP is almost identical in the scanning angle of 0 ° and 90 °, Represent and there is no preferably lattice direction in non-PIF PP.PP test piece is through PIF step (PIF condition：110 DEG C, 400MPa) difference afterwards Substantially, represent and create directional crystal structure in this step in material.This is that whole spherocrystal deforms and is related to flaky crystal (lamellae) positive evidence.In general, symmetrical spherocrystal shape becomes the shape of the direction elongation along flowing.
When PP granule is coated with through MWCNT, this MWCNT coating layer also can flow along PIF direction under high pressure.Should MWCNT coating layer orients along PIF direction and forms clearly co-continuous " brick and mud " structure.Here, this macroscopic " brick and The PP resin (" mud ") by MWCNT coating layer (" brick ") and in this coating layer for the mud " structure is formed；And the PP of orientation For " brick ", nondirectional region is " brick and mud " structure of the macroscopic of " mud " to crystal.Relatively conventional have same composition composition For complex, this unique " brick and mud " structure can provide excellent machinery and physical property, or even greatly improves eutectic Melt the not good shortcoming of intensity PP foaminess.
According to the above results, the application of high pressure can be in the solid state in semi-crystalline polymer and block copolymer system Induction class melt behavior is to form " brick and mud " structure.When those materials are placed under stress, rigid plastics start to melt And deliquescing, create the mixture of flowing as the serosity including ice and water, make material be molded as given shape.When During pressure release, plastics are rehardened.Crystal structure in semi-crystalline polymer (as PP) also deforms in this PIF step.Ball Crystalline substance can experience very big deformation, and its flaky crystal rupturable become small pieces being scattered in each other in equatorial zone (equatorial region)；But at polar region (polar region), flaky crystal system orientation is to deform parallel to extensive Appendix direction.
Mechanical property
PP intensity very low (data is not shown) through CNTs coating, but PIF can significantly increase its mechanical property.Figure 13A compares the tension intensity of the PP and PP/MWCNT complex through PIF and without PIF.With pure PP, through compression molding be obtained answer Close PP/MWCNT test piece to compare, through PIF can make tension intensity increase above 250% respectively (>250%) and more than 50% (> 50%).The tension intensity of the PP being obtained through PIF is also higher than twin shaft and extends PP, and its intensity is higher than injection molding PP.Figure 13 B compares Bending strength between identical test piece.Similarly, have " brick and mud " structure PP/MWCNT nano-complex have outstanding Performance.The compound PP/MWCNT test piece be obtained compared to pure PP and via injection molding, the bending of the test piece being obtained through PIF Intensity increase above 60% respectively (>60%) and more than 25% (>25%).In Izod impact strength (Izod impact Strength more preferably obvious difference) can be observed, as shown in fig. 13 c.The PP/MWCNT nanometer with " brick and mud " structure is multiple Compound intensity is the 500% of pure PP test piece, and better than compound PP/MWCNT, more than 40% (>40%).
UAPIF allows engineering propertiess have similar lifting, but its required pressure ratio PIF is come low.In different PP and PP/ In MWCNT test piece, reach the Ultrasonic Conditions required for 200% deformation and be shown in table 4 below, wherein, 400MPa, 110 DEG C When through PIF step process PP test piece deformation be set as 200%.
Table 4
Upper table 4 result display ultrasonic pressure is higher, and the required time is shorter.As long as several seconds of required sonication times Clock, compared to traditional PIF step, import ultrasonic activation can efficiently reduce desirable pressure reach at least an order of magnitude (by 400MPa to 10-30MPa).For PP/MWCNT nano composite material, when needing longer step under ultrasonic pressure Between (more multi-energy) reaching the deformation of same degree.Additionally, being combined compared to PP/MWCNT, the nanometer through PP/MWCNT coating Complex needs the time (more multi-energy) slightly grown.
Figure 14 compares after UAPIF, and pure PP, PP/MWCNT 3wt%MWCNT is combined and PP/MWCNT 3wt%MWCNT The bending stress of coated sample.Such as PIF, UAPIF step improves the bending stress of PP test piece with can dramatically.After UAPIF, tool The intensity having the PP/MWCNT nano-complex of " brick and mud " structure be better than pure PP sample more than 70% (>, and be better than 70%) 3wt% be combined PP/MWCNT more than 25% (>25%).The UAPIF step with relatively low pressure is for large-scale PP/MWCNT Complex manufactures and lifts its characteristic is favourable.
Additionally, the temperature change of PP test piece is also tested in this together under UAPIF, result is as indicated in fig. 12 c.Although Ultrasound wave can heat sample, but when mold temperature set is 110 DEG C, maximum temperature is less than PP fusing point, and in other words, ultrasound wave will not Fusing brick and mud structure.Additionally, the result that Figure 12 A shows be further characterized by through UAPIF process PP test piece fusion temperature and Degree of crystallinity is again similar to the PP of the process through PIF.If however, mold temperature, moulding pressure or ultrasonic intensity are too high When, in UAPIF process it may happen that fusing, mechanical property will be led to reduce, as shown in Figure 19 A and 19B.Therefore, select Good UAPIF condition is important.
The precise mechanism why ultrasound wave can substantially reduce the pressure needed for PIF is not clear at present.However, we Propose explained below：In order to " brick and mud " structure will be formed under solid state PIF, need enough pressure with from elastomeric Transfer to rigid crystals region in amorphous phase, and lead to the latter's deformation or orient.Because can be relative to each other between texture area Slide, rather than deformed or orient, therefore need very high static pressure under PIF to produce enough pressure.On the other hand, surpass The PIF of sound wave auxiliary, the pressure propagation through rubber-like amorphous phase can more efficiently and relatively rare texture area be slided, therefore Required pressure is less than PIF pressure.
Aforementioned result display ultrasound wave can reduce required pressure in PIF step.Even if however, not leading in PIF step Enter ultrasound wave, the crystalline region of PP or PP/MWCNT complex still can deform and be changed into " brick and mud " structure.
As PP, the compound PP/MWCNT test piece with 3wt% nano-particle is nonconducting.And the PP through MWCNT coating Test piece is conductive because forming " brick and mud " co-continuous structure.The PP resistance with 3wt%MWCNT coating is about 0.55k Ω.UAPIF somewhat increases resistance to 0.9k Ω.In compound PP/MWCNT complex, need enough MWCNTs to reach conduction Percolation threshold (percolation threshold).On the other hand, in the PP/MWCNT complex that PIF and UAPIF is obtained The co-continuous structure of honeycomb the test piece with 3wt%MWCNT can be made to have electric conductivity, this is because in whole test piece, The reason that MWCNTs is interconnected amongst one another and forms conductive channel.
The foam performance of PP/MWCNT " brick and mud " structural composites
The major defect of the test piece being formed through PIF and UAPIF is high residual stress (residual stress).As figure Shown in 18A and 18B, during heat treatment, the PP of extension shrinks in the flowing direction and launches in vertical direction, leads to serious examination Piece warpage.However, this test piece warpage does not result in very big impact for the foaming capacity of micro-pore of polymer.
Using supercritical carbon dioxide (scCO2) solid-state batch foaming step, with multiple from " brick and mud " structure preparation PP Compound foaming body.In many foam application, CO2As physical blowing agent, because its many advantageous feature (that is, nonflammable, Nontoxic, cheap and have relatively high dissolubility in polymer) and may replace the use of ozone layer depletion fluorine foaming agent.
During solid-state foaming, remaining pressure can completely be released.Additionally, in 150 DEG C, 13.8MPa CO2See during pressure Observe the bimodal foam structure of special successively (layer by layer), it has micro structure foam size (data is not shown). In comparison, in the PP of pure PP and the compound MWCNT of tool 3wt%, the foam of only minority is formed.Have relatively through the test piece that PIF is processed Low density, the foaming body density being formed is 0.65-0.86g/cm3, as shown in table 5 below.
Table 5
Due to the melt strength of PP low it is difficult to realize there is uniform foam structure and the foaming body of low apparent specific gravity (gd)；So And above-mentioned restriction can be overcome through " brick and mud " structure produced by PIF.As shown in figure 15, in 155 DEG C, 13.8MPa CO2Pressure When, compared to PIF-PP test piece (22.5), lower expansion ratio (6) is had by the foaming body that pure PP is obtained.Additionally, from SEM (data is not shown), in 155 DEG C, 13.9MPa CO2Free foaming during pressure and prepared low-density (0.039g/mL) PIF- PP/MWCNT 3wt% is coated with the bimodal foaming structure that nano-complex foaming body has successively (layer by layer).? 155 DEG C of foaming cause the change of crystal after foaming.Degree of crystallinity is reduced to 18.3% from 32%, and has β-cylindrites shape Become.It is interesting that the PP that in PIF, solid-state foaming is obtained can improve its heat stability, as shown in figure 16.
In solid-state batch foaming step, crystalline texture can affect foam nucleation and growth simultaneously.In foam nucleating step In, it is a high energy region between the interface of flaky crystal and non-crystalline areas, the wherein Ji Bu needed for one stable foam of nucleation This free energy (Gibbs free energy) is less than the Gibbs free energy of homogeneous nucleation, is therefore inclined to and preferentially becomes at this interface The stable foam of core.When this foam grows, because few in crystal region molecular link mobility, the foam being formed is by adjacent Flaky crystal limits.When blowing temperature is higher than 155 DEG C, because the fusing of " brick and mud " structure, lead to CO2The fusing of saturation PP Expansion ratio difference such as Figure 15 between temperature, pure PP and PIF-PP.
The compression stress of the pure PP of solid and the PP foaming body derived from different PP/MWCNT complex and dependent variable such as Figure 17 A Shown., (density is 0.76g/cm to pure PP taking 10% compressive strain as a example3) foaming body compressive strength only about 10MPa, be (density is 0.9g/cm to solid PP3) about 25%.However, having 0.66g/cm3The compressive strength of low-density PIF-PP can Reach 25MPa, simultaneously through PIF step and through PP/MWCNT coating nano-complex foaming body (there is similar density) then close to solid Body PP.
In 155 DEG C of high-foaming temperature and 13.9MPa CO2PP/MWCNT complex during pressure, through PIF or without PIF Expansion density difference as shown in table 6 below.The density of pure PP foaming body>0.15g/cm3, and have MWCNT nano-particle or do not have The test piece being obtained via PIF of MWCNT nano-particle, its density is about 0.037-0.04g/cm3.3wt% without PIF is combined And the foaming test piece of coating MWCNT has similar density (0.18-0.24g/cm to the pure PP foaming body without PIF3), represent " brick and mud " structure, and non-nanoparticulate, are the Main Factors controlling expansion ratio." brick and mud " structure can prevent CO2Expand Shed test piece, and assists to support that the foam being formed does not cave in.
Table 6
Figure 17 B compares through PIF and answers without the compression of the low-density of PIF pure PP and PP/MWCNT nano-complex foaming body Power and compressive strain.When 155 DEG C, the density of foaming body is：Pure PP：0.15g/cm3；PIF-PP：0.037g/cm3；PIF- PP/MWCNT 3wt% coating：0.04g/cm3；And PIF-PP/MWCNT 3wt% is combined：0.04g/cm3.Although pure PP's is close Degree has 2.5 to 2.7 times of the foaming body test piece of " brick and mud " structure higher than remaining, but the compression stress of pure PP foaming body is minimum 's.Obviously, lead to " brick and mud " structure of foam structure that is less and closing, above-mentioned obvious performance boost is contributed good Many.Under PIF, compared to composite specimen, the foaming body including coating MWCNT provides more preferable compression property, may be owing to It has the reason of bimodal foam structure successively.
In sum, the PP/MWCNT nano-complex system with " brick and mud " structure is coated with by little PP granule MWCNT, then carries out PIF or UAPIF step and is obtained.UAPIF step can reduce required PIF pressure, and kenel and characteristic Can compare favourably with carrying out PIF step, but ultrasound wave is not required in that in the present invention.Additionally, after PIF or UAPIF step " the brick and mud " structure obtaining also can improve the foaminess of low melt strength PP, and is not having any physically or chemically additive In the case of produce low density foaming agent.Have coating MWCNT when, should " brick and mud " structure foaming body was had successively Bimodal foam structure.Compared to traditional foaming body with same composition composition, this foaming body can provide excellent engineering propertiess And more preferable heat stability, and it is conductive.
In a word, can be found that by the result of embodiment 1 and embodiment 2, if having Ultrasound-assisted PIF process be prepare poly- The committed step of compound foaming body, because PIF polymer sheet has holding CO2And avoid CO2From the effusion of PIF polymer sheet Ability；And therefore, can obtain in shorter foamed time and there is low-density micro-pore of polymer.
Particular embodiments described above, has been carried out further specifically to the purpose of the present invention, technical scheme and beneficial effect Bright be not limited to the present invention it should be understood that the foregoing is only the specific embodiment of the present invention, all at this Within bright spirit and principle, any modification, equivalent substitution and improvement done etc., should be included in protection scope of the present invention Within.

Claims (26)

1. a kind of method preparing micro-pore of polymer is it is characterised in that comprise the following steps：
One polymer body is provided；
Under one first specified temp and one first specified pressure, hold the pressure time in one, a pressure is carried out on this polymer body Power induced flow (pressure-induced flow, PIF) step is obtaining a polymer sheet；And
Under one second specified temp and one second specified pressure, in a saturation time, this polymer sheet injects one Foaming agent carries out a foaming step and obtains a micro-pore of polymer.
2. method according to claim 1 is it is characterised in that wherein this first specified temp is less than this polymer body Fusing point.
3. method according to claim 1 is it is characterised in that wherein this first specified temp is between 100 DEG C to 160 ℃.
4. method according to claim 1 is it is characterised in that wherein this first specified pressure is between 20MPa extremely 420MPa.
5. method according to claim 1 is it is characterised in that wherein this holds the pressure time is between 10 seconds to 300 seconds.
6. method according to claim 1 is it is characterised in that wherein this second specified temp is between 130 DEG C to 160 ℃.
7. method according to claim 1 is it is characterised in that wherein this second specified pressure is between 11.7MPa extremely 17.3MPa.
8. method according to claim 1 is it is characterised in that wherein this saturation time is between 10 minutes to 120 minutes.
9. method according to claim 1 it is characterised in that wherein this polymer body be semicrystalline thermoplastics or Thermoplastic elastomer (TPE).
10. method according to claim 1 is it is characterised in that wherein this polymer body includes at least one selected from poly- Ethylene (polyethylene), polypropylene (polypropylene), polrvinyl chloride (polyvinyl chloride), poly- carbonic acid Ester (polycarbonates), polyamide (polyamides), polyethylene terephthalate (polyethylene Terephthalate), polybutylene terephthalate (polybutylene terephthalate) and polylactic acid The group that (polylactic acid) is formed.
11. methods according to claim 1 it is characterised in that wherein this foaming agent be pentane, isopentane, Pentamethylene., CO2、N2, nitrogen system expanded material or a combination thereof.
12. methods according to claim 11 are it is characterised in that wherein this foaming agent is supercritical carbon dioxide.
13. methods according to claim 1 are it is characterised in that wherein this polymer body is one to include polymer beads And a complex of coating material, and the surface of this polymer beads is coated with through this coating material.
14. methods according to claim 13 are it is characterised in that wherein this complex is with the following step preparation：
There is provided and mix this polymer beads and this coating material to obtain a mixture；And
Heat this mixture to obtain this complex.
15. methods according to claim 13 are it is characterised in that wherein this polymer beads and this coating material is to be situated between Mix at a temperature of between 140 DEG C to 160 DEG C.
16. methods according to claim 13 are it is characterised in that wherein this mixture is between 100 DEG C to 300 DEG C One at a temperature of heat.
17. methods according to claim 13 are it is characterised in that wherein this mixture is between 11.7MPa extremely Heat under a pressure between 17.3MPa.
18. methods according to claim 13 are it is characterised in that wherein this coating material is an organic substance, inorganic Material or a combination thereof.
19. methods according to claim 18 are it is characterised in that wherein this coating material is at least one selected from carbon nanometer Pipe, Graphene, graphene oxide, carbon black, carbon nano-fiber, graphite, carbon particulate, clay, Muscovitum, glass fibre, silicate, Metal particle, SiO2, MgO, CaO, Pulvis Talci, TiO2, the group that formed of ZnO and MnO.
20. methods according to claim 1 are it is characterised in that wherein this pressure-induced flow (PIF) step is one ultrasonic Ripple aux. pressure induced flow (PIF) step.
A kind of 21. micro-pore of polymers are it is characterised in that include：
One polymer body, has multiple foams in this polymer body；
Wherein this micro-pore of polymer has expansion density between 0.03g/cm3To 0.25g/cm3；And
When the compressive strain of this micro-pore of polymer is between 10% to 70%, this micro-pore of polymer has 0.2MPa extremely The compressive strength of 0.7MPa.
22. micro-pore of polymers according to claim 21 are it is characterised in that wherein when this micro-pore of polymer is placed in When under conditions of 120 DEG C, the absolute value of this micro-pore of polymer change in size is between 0% to 60%.
23. micro-pore of polymers according to claim 21 it is characterised in that wherein this polymer have degree of crystallinity between 10% to 30%.
24. micro-pore of polymers according to claim 21 are it is characterised in that wherein foaming body has 200 μm to 300 μm Average cell size.
25. micro-pore of polymers according to claim 21 are it is characterised in that wherein this polymer body is one to include gathering Polymer beads and a complex of coating material, and the surface of this polymer beads is coated with through this coating material；Wherein this bubble Body is formed in this polymer beads.
26. micro-pore of polymers according to claim 21 are it is characterised in that wherein this polymer body includes pure poly- third Alkene (neat PP).
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118538A (en) * 2017-05-05 2017-09-01 宁波格林美孚新材料科技有限公司 A kind of preparation method of thermoplastic elastomer (TPE)/conductive fiber composite foam material
CN107177191A (en) * 2017-05-05 2017-09-19 宁波格林美孚新材料科技有限公司 A kind of moulding process of thermoplastic elastomer (TPE)/carbon fiber composite foam material
CN110405999A (en) * 2019-07-31 2019-11-05 太仓富宇塑胶科技有限公司 The good EPP preparation method of deformation buffer performance
CN111331770A (en) * 2020-03-04 2020-06-26 山东大学 Carbon material modification-based foaming injection molding preparation of thermoplastic elastomer flexible foam product, preparation method and molding system
CN111574745A (en) * 2020-06-11 2020-08-25 湖北工业大学 High-strength super-toughness polylactic acid nano-pore foaming material and preparation method thereof
CN112020679A (en) * 2018-04-18 2020-12-01 佳能株式会社 Conductive member, process for producing the same, process cartridge, and electrophotographic image forming apparatus
CN114031805A (en) * 2021-08-26 2022-02-11 浙江工业大学 Preparation method of PIF foamed polymer sound insulation material
US11640122B2 (en) 2018-04-18 2023-05-02 Canon Kabushiki Kaisha Electroconductive member, process cartridge, and image forming apparatus
US11971683B2 (en) 2019-03-29 2024-04-30 Canon Kabushiki Kaisha Electrophotographic electro-conductive member, process cartridge, and electrophotographic image forming apparatus

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107522942B (en) * 2017-08-04 2020-09-08 浙江新恒泰新材料有限公司 Conductive polypropylene microporous foam material and production method thereof
WO2019064121A1 (en) * 2017-09-29 2019-04-04 3M Innovative Properties Company Polymeric foam layer and methods of making the same
CN108384119B (en) * 2018-03-28 2020-11-17 广州捷佛明新材料科技有限公司 Polypropylene foaming material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101146852A (en) * 2005-03-22 2008-03-19 普瑞曼聚合物有限公司 Extruded propylene resin foam and process for production thereof
CN102229708A (en) * 2011-05-16 2011-11-02 四川大学 High foaming-ratio and high-density polyethylene microporous foaming section bar and its preparation method
CN103153572A (en) * 2010-09-22 2013-06-12 巴斯夫欧洲公司 Fixing of vacuum insulation panels in cooling apparatuses
CN104327373A (en) * 2014-10-08 2015-02-04 浙江工业大学 Preparation method for polymer base nanometer composite material with highly oriented nanoparticles in polymer matrix

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101146852A (en) * 2005-03-22 2008-03-19 普瑞曼聚合物有限公司 Extruded propylene resin foam and process for production thereof
CN103153572A (en) * 2010-09-22 2013-06-12 巴斯夫欧洲公司 Fixing of vacuum insulation panels in cooling apparatuses
CN102229708A (en) * 2011-05-16 2011-11-02 四川大学 High foaming-ratio and high-density polyethylene microporous foaming section bar and its preparation method
CN104327373A (en) * 2014-10-08 2015-02-04 浙江工业大学 Preparation method for polymer base nanometer composite material with highly oriented nanoparticles in polymer matrix

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BAO JIN-BIAO等: "Supercritical carbon dioxide induced foaming of highly oriented isotactic polypropylene", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 *
HUAN QIAN等: "Markedly improving mechanical properties for isotactic polypropylene with large-size spherulites by pressure-induced flow processing", 《POLYMER》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118538A (en) * 2017-05-05 2017-09-01 宁波格林美孚新材料科技有限公司 A kind of preparation method of thermoplastic elastomer (TPE)/conductive fiber composite foam material
CN107177191A (en) * 2017-05-05 2017-09-19 宁波格林美孚新材料科技有限公司 A kind of moulding process of thermoplastic elastomer (TPE)/carbon fiber composite foam material
CN112020679A (en) * 2018-04-18 2020-12-01 佳能株式会社 Conductive member, process for producing the same, process cartridge, and electrophotographic image forming apparatus
CN112020679B (en) * 2018-04-18 2022-10-14 佳能株式会社 Conductive member, process for producing the same, process cartridge, and electrophotographic image forming apparatus
US11640122B2 (en) 2018-04-18 2023-05-02 Canon Kabushiki Kaisha Electroconductive member, process cartridge, and image forming apparatus
US11971683B2 (en) 2019-03-29 2024-04-30 Canon Kabushiki Kaisha Electrophotographic electro-conductive member, process cartridge, and electrophotographic image forming apparatus
CN110405999A (en) * 2019-07-31 2019-11-05 太仓富宇塑胶科技有限公司 The good EPP preparation method of deformation buffer performance
CN111331770A (en) * 2020-03-04 2020-06-26 山东大学 Carbon material modification-based foaming injection molding preparation of thermoplastic elastomer flexible foam product, preparation method and molding system
CN111331770B (en) * 2020-03-04 2021-12-03 山东大学 Carbon material modification-based foaming injection molding preparation of thermoplastic elastomer flexible foam product, preparation method and molding system
CN111574745A (en) * 2020-06-11 2020-08-25 湖北工业大学 High-strength super-toughness polylactic acid nano-pore foaming material and preparation method thereof
CN111574745B (en) * 2020-06-11 2022-04-22 湖北工业大学 High-strength super-toughness polylactic acid nano-pore foaming material and preparation method thereof
CN114031805A (en) * 2021-08-26 2022-02-11 浙江工业大学 Preparation method of PIF foamed polymer sound insulation material

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